EP2304828A1 - Mélange d'oxydes contenant un spinelle lithium-manganèse et son procédé de fabrication - Google Patents
Mélange d'oxydes contenant un spinelle lithium-manganèse et son procédé de fabricationInfo
- Publication number
- EP2304828A1 EP2304828A1 EP09768968A EP09768968A EP2304828A1 EP 2304828 A1 EP2304828 A1 EP 2304828A1 EP 09768968 A EP09768968 A EP 09768968A EP 09768968 A EP09768968 A EP 09768968A EP 2304828 A1 EP2304828 A1 EP 2304828A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- manganese
- mixed oxide
- lithium
- boron
- mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 77
- 239000011029 spinel Substances 0.000 title claims abstract description 77
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000008569 process Effects 0.000 title claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 68
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 39
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 35
- 229910052749 magnesium Inorganic materials 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical group [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 235000006748 manganese carbonate Nutrition 0.000 claims description 5
- 239000011656 manganese carbonate Substances 0.000 claims description 5
- 229940093474 manganese carbonate Drugs 0.000 claims description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000001033 granulometry Methods 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- -1 oxides Chemical class 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 8
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 229910052566 spinel group Inorganic materials 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- 239000011701 zinc Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000010949 copper Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 13
- 238000010348 incorporation Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 235000010338 boric acid Nutrition 0.000 description 7
- 229960002645 boric acid Drugs 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 229910018068 Li 2 O Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 4
- 150000002697 manganese compounds Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical class [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000011514 reflex Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010316 high energy milling Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 241000556720 Manga Species 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 210000001744 T-lymphocyte Anatomy 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical class [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/128—Borates containing plural metal or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/54—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [Mn2O4]-, e.g. Li(CoxMn2-x)04, Li(MyCoxMn2-x-y)O4
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Definitions
- the invention relates to a mixed oxide containing a mixed-doped lithium manganese spinel and a boron-oxygen compound and to a process for the preparation thereof and to the use thereof, in particular as cathode material in lithium ion secondary batteries.
- Rechargeable lithium ion batteries are characterized by high specific energy and performance. They are therefore preferably used in applications that require the lowest possible weight and a small footprint. Thus, for portable electronic devices, such. B. video cameras, laptop computers or mobile phones today mainly lithium ion secondary batteries used as energy storage. Further reducing the manufacturing costs of lithium rechargeable batteries, other potential applications are conceivable, such as e.g. cordless power tools, vehicle electrical systems, traction or hybrid batteries in vehicles, or even in stationary applications, e.g. for emergency power supply devices.
- the operating principle of today's lithium-ion batteries is based on the use of electrode materials that can reversibly intercalate lithium.
- carbon compounds are commonly used as the anode and a lithium-containing oxide as the cathode.
- the lithium at Potentials between 3 and 4 V vs. Li / Li + can intercalate.
- the most promising materials that meet these requirements are lithium compounds based on cobalt, nickel, iron and manganese oxides. For reasons of cost, environmental friendliness and application safety, manganese and iron based materials are currently preferred.
- LiMn 2 O 4 sinometric spinel
- Li 2 Mn 4 O 9 oxygen-rich spinel
- Li 4 Mn 5 Oi 2 lithium-rich spinel
- these spinels are produced by means of solid-state reactions. This usually results in stoichiometric spinels, but usually have only an insufficient cycle life. This is attributed to changes and defects in the lattice structure that occur during the installation and removal of lithium ions.
- US Pat. No. 4,507,371 describes an electrochemical cell in which the anode, electrolyte or cathode each have a material which has a cubic close-packed frame structure which has as structural unit a unit of the formula (B 2 ) X 4 " ' and the structural unit of an A ( B 2 ) X 4 spinel is.
- the structure absorbs active cations M + that can diffuse within this structure.
- This document also describes the forms of crystal defects and stoichiometric deviations known in structural chemistry for type AB 2 X 4 spinel structures, such as the partial replacement of B cations with A cations or the deficiency or excess of X anions, and teaches these can not take a more precisely quantified influence on the electrochemical properties.
- the US 5,316,877 describes spinel compounds of the general formula LiiD x / bMn 2-x 0 4+ ⁇ with 0 ⁇ x ⁇ 0.33; 0 ⁇ ⁇ ⁇ 0.5; where D is preferably Li, Mg, Co, and b is the oxidation state of this cation is.
- the preparation is carried out by a solid-state process, in which LiNO 3 , or LiOH with ⁇ -MnO 2 in the desired molar ratio are mixed together with hexane in a ball mill. The mixture is then calcined for 48 h in air at 450 0 C and calcined for a further 48 h at 750 0 C.
- EP 0 783 459 B1 describes doped lithium complex oxides of the general formula Li y Me x Mn 2 - ⁇ 4 , which have a spinel-type crystal structure and are suitable as cathode material in lithium secondary batteries.
- the batteries made with these cathodes should show a good cycle life.
- the lithium-manganese spinel is prepared by reacting with the stoichiometry of the spinel to be prepared corresponding amounts of the reaction components in the form of hydroxides and / or water-soluble metal salts in dissolved form in a basic aqueous medium to form a homogeneous suspension.
- the dried reaction products are then heated at a heating rate of 1-20 K / min to temperatures between 500 and 900 0 C, wherein the respective mixed oxides form in X-ray phase-pure form.
- Particularly suitable metal cations Me are iron, titanium and aluminum as well as cobalt and nickel.
- complex oxides of the formulas LiFe 0 Mn 119 O 4 , LiTi 0 , l Ntai, g ⁇ 4 and LiNi 0 ,! Mn ⁇ 5 O 4 disclosed.
- the patent teaches that a uniform fine distribution of the starting components is important for the production of phase-pure doped lithium manganese spinels and that this fine distribution is achieved particularly advantageously by the co-precipitation of the starting components from a solution.
- the compound has the following general formula: Li x Mn 12 - Y) M y I B y 2 O 4 ,
- the doping element boron is added because of its easy solubility in the second process step and is installed on the lattice sites of manganese.
- Robertson et al. J. Electrochem Soc., 144, 10, (1997), 3500-3512 report a boron-doped spinel of the composition LiMn 1 , 98 Bo, o 2 ⁇ 4 of enlarged crystallites (around 1 ⁇ m) and a reduced specific surface area BET ( ⁇ 1 m 2 / g).
- the corresponding scanning electron micrograph shows large octahedral crystallites with rounded corners and edges with indicated crystal surfaces.
- very poor electrochemical properties are also reported for this material.
- a specific capacity of less than 50 mAh / g was measured, which also greatly decreases from cycle to cycle.
- EP 1 204 601 Bl lithium manganese spinels for thin film electrodes are described. In the process of EP 1 204 601
- Bl is the resulting lithium manganese spinel in the form of
- EP 0 993 058 A1 describes a lithium secondary battery whose active material of the positive electrode is composed essentially of lithium and manganese and has a cubic spinel structure.
- Boron-doped LiMn 2 O 4 is used as the electrode material.
- JP 2001-48545 a process for the preparation of a complex boron-doped lithium manganese oxide with spinel structure is described, wherein a lithium compound and a
- Aluminum is used in the form of a solid compound. Approximately spherical granulated particles having an average particle diameter of 15 ⁇ m are obtained.
- EP 1 136 446 A2 discloses coated lithium complex oxide particles and processes for their preparation.
- the coating which may be formed as a single or as several identical or different layers, is intended to improve the properties of electrochemical cells in which a cathode of the coated lithium manganese oxide material according to the invention consists.
- doping with additional lithium is described in the overall disclosure, it is not explicitly disclosed.
- Typical coatings are obtained with alkali borates and boron lithium complex salts.
- Li (Mn 2 - X Li x) O 4 which can be obtained by a spray pyrolysis method.
- Lithium is thereby incorporated instead of manganese on its 16d lattice sites, however, the lithium doping is limited to the range 0 ⁇ x ⁇ 0.05, since outside this range, the cycle characteristic of cathodes containing this material due to the Jahn-Teller effect opposite the unsubstituted lithium manganese spinels deteriorated.
- US Pat. No. 7,217,406 describes granular particles of a lithium manganese oxide for use as material in secondary batteries, in which boron, in particular H 3 BO 3 , is added as a so-called "flux". Boron is incorporated in place of the manganese at its lattice sites.
- Lithium secondary batteries are also increasingly used in applications in which a long cycle life, a high current carrying capacity and high security in case of abuse or
- the invention was therefore based on the object of providing a material, in particular a material containing a lithium manganese spinel, which can be used as electrode material, in particular in secondary lithium ion batteries, and has good charging characteristics.
- the mixed oxide according to the invention has improved electrochemical properties compared with a lithium-manganese spinel doped with foreign atoms such as Zn, Mg, Cu, Al or with a lithium-stoichiometrically doped lithium-doped spinel.
- a lithium-manganese spinel doped with foreign atoms such as Zn, Mg, Cu, Al or with a lithium-stoichiometrically doped lithium-doped spinel.
- Manganese spinel or such a spinel doped with other impurities are examples of other impurities.
- mixed oxide denotes a homo-type home-type mixed crystal of the two
- the boron of the boron-oxygen compound is not a doping element for the 16 d manganese nitride sites in the lithium manganese spinel and does not occupy these sites. In this case, the compound would be a so-called "complex" oxide.
- mixed substituted means that besides (superstoichiometric) lithium, at least one other metal is located on the 16 d lattice sites of manganese other than manganese.
- Component a) of the mixed oxide according to the invention is typically also referred to as so-called “superstoichiometric" lithium manganese spinel.
- the homophasic mixed oxide according to the invention has a lower BET surface area than comparable lithium-manganese spinels doped with lithium and / or with metals or transition metals or pure lithium manganese spinels, namely a BET surface area of ⁇ 4 m 2 / g, preferably ⁇ 2 m 2 / g and more preferably ⁇ 1 m 2 / g and most preferably ⁇ 0.5 m 2 / g, which also significantly reduces the manganese dissolution in the electrolyte of a corresponding cell, since the BET surface area is correlated with the manganese dissolution in the electrolyte.
- the resistance to dissolution in the electrolyte is thus reduced by the mixed oxide according to the invention, i. in particular, therefore, by the presence of the boron-oxygen bond increases ⁇ vide infra).
- the presence of the boron-oxygen compound in the mixed oxide according to the invention surprisingly ensures a significantly increased homogeneity of the transition metal incorporation in the lithium manganese spinel compared to a doping without the presence of a boron-oxygen compound, so that in particular a homogeneous uniform incorporation of, for example, aluminum , Zinc etc. on the 16 d Mangangitter josn takes place. This also leads to significantly improved electrochemical properties.
- further manganese lattice sites (16 d position) in the lithium manganese spinel of the mixed oxide are preferred by at least one metal ion selected from the group consisting of Al, Mg, Zn, Co, Ni, Cu and Cr or mixtures thereof occupied or substituted, so that a large Variety of mixed substituted superstoichiometric lithium manganese spinels can be provided in the mixed oxide according to the invention, which can be optimized in particular with regard to the cycle stability.
- the presence of the boron-oxygen compound leads to extremely homogeneous incorporation of these metals on the manganese lattice sites.
- Part of the lithium ions on the 8a tetrahedral sites is further substituted by a metal ion selected from the group consisting of Zn, Mg and Cu, whereby the electrochemical properties of the mixed oxide according to the invention can be adjusted even more precisely.
- the boron-oxygen compound in the mixed oxide according to the invention is preferably a boric oxide or a boric acid, most preferably B 2 O 3 or H 3 BO 3 .
- Further representatives of these classes of compounds which can be used according to the invention are (BO) x , BO, B 2 O and H 2 BO 2 and HBO.
- borates ie the salts of orthoboric acid (H 3 BO 3 ) and of metaboric acid (H 2 BO 2 ), preferably monoborates.
- oligo- and polyborates may also be used.
- alkali metal metaborates M 2 BO 2 in particular Li 2 BO 2 .
- the mixed oxide according to the invention has the following advantages over pure doped or non-doped lithium manganese spinels without the presence of boron-oxygen compounds:
- the mixed oxide according to the invention has a greatly reduced BET surface area of ⁇ 0.5 m 2 / g, the BET surface area correlating with the manganese dissolution in the electrolyte.
- the mixed oxide according to the invention has an increased tap density (increase from 1.23 g / cm 3 to 2.03 g / cm 3 ).
- the mixed oxide according to the invention has narrow reflection widths in the XRD spectrum and large crystallites.
- the homogeneity of the doping metal incorporation in the spinel of the mixed oxide is markedly improved compared to doped lithium manganese spinel of the prior art.
- the lithium manganese spinel of the mixed oxide contains the lithium on a part of the manganese nitride sites (superstoichiometry).
- the doping metal ions are distributed uniformly in the crystal. This is evident, for example, in the oxidation state of manganese and in the X-ray diffraction spectrum (see examples below).
- the amount of lithium in the mixed oxide according to the invention must be increased in order to produce electrodes with electrochemically particularly advantageous properties.
- additional Li in the molar ratio f Li / B of 1 to 4 to 1 must be added. This ratio is preferably 1 to 3 to 1 and more preferably 1.5 to 3 to 1.
- the general formula of the mixed oxide according to the invention can be represented as follows: [(LII a M.) (Mn 2 - cd Li c N d) O x] -b (B z O y H u X v) (I)
- M is at least one element from the group of Zn, Mg and Cu;
- N is at least one element from the group of Al, Mg, Co, Ni, Cu and Cr;
- X is at least one element from the group Li, Na, K.
- M is at least one element from the group of Zn, Mg and Cu;
- N is at least one element from the group of Al, Mg, Co, Ni, Cu and Cr.
- the amount of boron-oxygen compound in the mixed oxide is chosen so that the formula coefficient b defined above is between 0.01 and 0.05, preferably between 0.01 and 0.05, very particularly preferably between 0.0025 and 0.025 and still more preferably between 0.005 and 0.0025.
- the lithium manganese spinel of the mixed oxide according to the invention has a very uniform distribution of the doping elements N in the crystal lattice. Furthermore, the mixed oxide of the invention shows a very high phase purity, which is reflected also in the X-ray diffraction spectrum.
- the mixed oxide according to the invention preferably has a signal at a diffraction angle of 2 ⁇ in the range from 63.5 to 65 °, in which the ratio of line width Bi 0 measured in 10% of the signal height to line width B 50 measured in 50% of Signal height, of less than 2.0, preferably less than 1.8.
- the diffraction signal shows no shoulder, indicating a high phase purity (see Figures 1 and 5).
- the superstoichiometric lithium is, as already stated, incorporated into lattice sites of manganese in the lithium manganese spinel according to the invention. This is shown by the degree of oxidation of manganese.
- the manganese of the spinel in the mixed oxide according to the invention preferably has an oxidation degree, determined by cerimetry, in the range from 3.60 to 3.69.
- the mixed oxide according to the invention has comparatively large particles, with the lithium manganese spinel contained in the mixed oxide having few defects. This advantageously results in a small BET area.
- the mixed oxide according to the invention preferably has a BET surface area determined in accordance with DIN 66132 of less than 4 m 2 / g.
- the mixed oxide according to the invention has a relatively high particle size.
- the size of the primary crystallites is preferably at least 0.5 ⁇ m, preferably ⁇ 1 ⁇ m, most preferably in the range between 1 and 3 ⁇ m.
- the size of the primary crystallites can be determined under the electron microscope (see FIG.
- a proportion of doping elements N is preferred in which the value of d is in the range of 0.05 to 0.2. Particularly preferred is a value for d ranging between 0.08 and 0.15.
- aluminum is used as doping element N of the mixed oxide according to the invention.
- magnesium is a further preferred doping element N or mixtures of aluminum and magnesium.
- a proportion is preferred which corresponds to a value of a from 0.005 to 0.02.
- Particularly preferred doping element M is zinc.
- the mixed oxide of the invention is very suitable as an electrode material for the production of secondary lithium batteries.
- the invention therefore also provides an electrode comprising an electrically conductive support on which the mixed oxide according to the invention is applied. It was a further object of the invention to provide a process for producing mixed oxides containing a doped or non-doped lithium manganese spinel which can be carried out economically and with which a mixed oxide containing lithium manganese spinel is obtained can be used as electrode material in powerful lithium secondary batteries.
- This object is achieved by a method for producing a mixed oxide containing a mixed doped lithium stoichiometric manganese spinel, wherein
- a second portion of a liquid mixture is prepared which contains a proportion of the components in dissolved form and / or as a suspension,
- M is at least one element from the group of Zn, Mg and Cu;
- N is at least one element from the group of Al, Mg, Co, Ni, Cu and Cr;
- X is at least one element from the group Li, Na, K;
- the mixture is calcined at a temperature of more than 300 0 C.
- a mixed oxide containing a doped superstoichiometric lithium manganese spinel and a boron-oxygen compound are first at least one compound of the elements Li, Mn and boron (here, of course, a boron-oxygen compound) and a compound a metal N, wherein N is selected from the group of Al, Mg, Co, Ni, Cu and Cr and / or a compound of a metal M, wherein M is selected from Zn, Mg and Cu.
- the starting components preferably the lithium or boron-oxygen component, may be provided in solid form.
- the boron-oxygen component is one of the boron-oxygen compounds described above.
- the solid components are preferably used in pre-milled form.
- the experiments have shown that the particle morphology of the mixed oxide can be controlled by the particle morphology of a solid and insoluble manganese compound used. Therefore, in a particularly preferred embodiment, a solid and insoluble manganese compound is used which has previously been brought to the desired particle size of the final product, which is determined by laser granulometry. This is essentially the limitation of the so-called oversize, which causes problems in the processing to thin film electrodes.
- the D95 value of a solid manganese compound used should therefore be less than 60 ⁇ m, preferably less than 30 ⁇ m. The method of determination is discussed below.
- the compounds are preferably each individually in the form of a
- At least one starting component namely preferably that of an inert doping element such as aluminum, magnesium, zinc, cobalt or nickel is dissolved in Form provided to ensure the fine distribution in the later process steps.
- the solvent is preferably water.
- the amount of solvent is chosen so that the components to be dissolved can be completely dissolved. Since the solvent must be removed again in a later process step, however, the amount of solvent is chosen as low as possible. However, the amount of solvent should be chosen so large that it can take up the solid components in the form of a suspension or paste. It is also possible to use all the starting components in dissolved form in order to create ideal conditions for their fine distribution in the later process steps. However, this is a less preferred embodiment because of the higher solvent requirement and because of the limitations on the choice of raw materials.
- the solid and dissolved components used for the preparation of the lithium manganese spinel-containing solid and dissolved components are preferably provided in the form of their nitrates, acetates, oxides, hydroxides or carbonates. These compounds are z. T. very well soluble in water.
- the soluble manganese component is preferably selected from manganese nitrate and manganese acetate.
- the solid manganese component is preferably selected from manganese carbonate, manganese oxide and manganese dioxide.
- the boron component is preferably selected from a boric acid, an alkali borate and a boron oxide.
- Typical representatives of boric acid are H 3 BO 3 , H 3 BO 2 , of oxides B 2 O 3 , (BO) x , BO 2 .
- Very particular preference is given to boric acid H 3 BO 3 and boron oxide B 2 O 3 as well as lithium or sodium borates.
- the manganese and boron components mentioned can be used individually or in a mixture.
- the stoichiometric amounts of the components are selected to be in a molar ratio corresponding to a mixed oxide of a doped lithium manganese spinel and a boron-oxygen compound of the following formula:
- M is at least one element from the group of Zn, Mg and Cu;
- N is at least one element from the group of Al, Mg 7 Co, Ni, Cu and Cr;
- X is at least one element from the group Li, Na, K.
- M is at least one element from the group of Zn, Mg and Cu;
- N is at least one element from the group of Al, Mg, Co, Ni, Cu and Cr.
- the mixing can be performed in any order.
- the liquid sub-mixture is initially introduced and the solid powdery sub-mixture is added with stirring, whereby a suspension or paste is obtained.
- a certain element is represented either only in the fixed part or only in the liquid part. But it can also be a particular element distributed to both shares.
- the manganese moiety is added both as a solid compound and as a dissolved compound in order to control both the particle morphology of the final product and to promote the homogeneous distribution of the inert doping elements.
- the mixture can be prepared in a conventional mixer.
- Components enters.
- the mixing of the components can at
- Temperatures from 0 ° to 100 0 C take place, but preferably between room temperature and 50 ° C. Depending on the mixing intensity of the mixing unit used mixing is carried out for a period of a few minutes to several hours.
- the mixing process preferably proceeds under chemical conditions in which compounds of the dissolved inert elements are precipitated. This can be done for example by changing the pH by one of the added components or by reacting two dissolved or one dissolved and one solid component with one another. But it is also possible to bring the dissolved inert components only during the subsequent drying to precipitate, but this is less advantageous for their uniform, fine distribution.
- the solvent is removed from the mixture.
- Any method can be used per se.
- the solvent can be removed by freeze drying or spray drying.
- the solvent may also be removed by heating the mixing vessel after mixing and distilling off the solvent with stirring.
- the mixture assumes a dough-like consistency, so that measures are taken if possible, which prevents the mixture from sticking to the mixer or the walls of the mixer tank.
- the mixture can for example also be transferred to an oven and there driven off at elevated temperature residual solvent.
- the temperatures are chosen so that the most uniform possible evaporation of the solvent is achieved. Preference is given to drying at temperatures of less than 300 ° C.
- the mixture is calcined at temperatures of 300 0 C to 800 0 C in air.
- the calcining is preferably carried out in two stages. The first stage is carried out at a holding temperature between 300 0 C and 600 0 C and for a period of 10min to 2h hours and serves the expulsion of gaseous decomposition products and the formation of a still little crystallized and immature spinel compound.
- the second stage is carried out as an annealing step at a holding temperature between 600 0 C and 800 0 C, preferably between 74O 0 C and 780 0 C, and for a period of 1 to 12 hours and serves to ripen the spinel compound.
- the heating rate is arbitrary, the cooling rate is preferably between 0.5 K / min and 5 K / min.
- the two temperature treatments may be consecutive or may be interrupted by an intermediate cooling step and a crushing treatment.
- the dissolved and precipitated components are uniformly distributed in the mixture and are thus evenly incorporated into the spinel, without the need for excessively high temperatures over a longer period for thermal treatment of the mixture must be used, as for example in pure solid process is the case.
- This increases the economics of the process through lower energy consumption and throughput, and reduces the losses of volatile lithium during the thermal treatment.
- a precipitation process with subsequent temperature treatment at a reduced holding temperature and holding time has the disadvantage of low crystallite sizes and a large specific surface area. This increases the attack surface against aggressive electrolyte components.
- the invention provides an additional addition of a boron-oxygen compound, so that a phase-pure mixed oxide is formed.
- a boron-oxygen compound in the process according to the invention not only promotes crystallite growth but, as already explained above, also the homogeneous distribution of the other doping elements.
- the distribution of the doping elements which can be qualified by evaluating the powder X-ray diffraction profiles of the end product in the spinel structure, is completely homogeneous in the process according to the invention both when using exclusively dissolved starting components and when predominantly using solid starting components, if a boron-oxygen compound is additionally added.
- the process according to the invention leads to a phase-pure mixed oxide in which boron, as stated above, occupies no lattice sites of manganese ("doping" or "substitution"), but rather than in the same phase as the doped lithium manganese spinel Boron-oxygen compound is present. This effect was previously unknown.
- the mixed oxides containing doped lithium manganese spinels according to the invention and a boron-oxygen compound can be prepared which have a comparatively large crystallite size and a low BET surface area.
- the dopants, the metals of the group formed by N and M are uniformly distributed on the manganese nitride sites in the spinel. Very uniform crystallites are obtained which have little lattice defect.
- the subject matter of the invention is a secondary battery, in particular a rechargeable secondary battery, which comprises an electrode containing the mixed oxide according to the invention as electrode material ("active material”), in particular cathode material.
- active material electrode material
- cathode material cathode material
- FIG. 1 shows the plot of dQ / dE versus E for different Co / Al / Li contents of lithium manganese spinels
- FIG. 2 XRD spectra of mixed oxides according to the invention and pure lithium manganese spinels in comparison
- FIG. 4 SEM images of mixed oxides according to the invention
- FIG. 5 Position, reflex width and phase purity of mixed oxides according to the invention
- FIG. 6 shows the influence of borate addition on the electrochemical behavior
- FIG. 7 shows the manganese dissolution of mixed oxides according to the invention in comparison with pure lithium manganese spinels in mg Mn / kg
- FIG. 8 the dependence of the BET surface area of mixed oxide crystals according to the invention on temperature and lithium superstoichiometry
- FIG. 9 shows the plot of dQ / dE versus E for mixed oxides according to the invention with different lithium excess stoichiometry
- FIG. 10 shows the discharge capacities of mixed crystals according to the invention in the first cycle
- FIG. 11 shows the potential curves in the first full cycle of mixed oxides according to the invention
- FIG. 12 shows the potential curves in the first full cycle of further mixed oxides according to the invention.
- FIG. 13 a scanning electron micrograph of a mixed oxide according to the invention containing lithium manganese spinel.
- Electrodes were prepared by mixing 70% of active material or composite oxide, 20% Timcl SuperlCl conductive carbon and 10% PTFE powder in a mortar, until a flake was formed. The flake was kneaded several times in the mortar before it was rolled out to a thickness of 100 microns in a stainless steel roller press. Round electrode foils with a diameter of 10 mm was gouged out, dried overnight at 200 0 C and then placed T-cell for electrochemical measurements in a Swagelock PVDF. The counter and reference electrodes consisted of a lithium metal foil and were separated by Whatman Whatman glass wool separator film. The electrolyte used was Merck LP30. The charge / discharge / test cycles were taken at a current of C / 20 and a nominal specific capacitance of 120 mA / h in a voltage window between 4.2 volts and 2.8 volts.
- the manganese carbonate and the aluminum nitrate nonahydrate are stirred or dissolved in a small amount in the submitted water with a laboratory anchor stirrer. Thereafter, the nitric acid is added slowly and stirring continued for 10min. The nitric acid is such that about 1/4 of manganese carbonate goes into solution as manganese nitrate.
- the laboratory anchor agitator is set at 40 rpm to keep the suspension in suspension.
- the powdered lithium hydroxide monohydrate is then added and the laboratory anchor agitator is set at 100 rpm for 30 minutes to compensate for the sharp increase in viscosity.
- the resulting medium brown paste is dried in the laboratory dish for 18 h at 100 0 C (weight 1431 g / weight 261 g) and crushed the brown drying product in a hand mortar.
- 51.1 g of dried product were in a ceramic crucible for Ih at 500 0 C calcined in a chamber furnace in air and thereby obtain 32.5 g of a black powder.
- 9.0 g of the calcination product were sintered in a ceramic furnace in the chamber furnace in air for 12 h at 750 0 C with a heating time of 6 h and a cooling time of also 6 h. In this case, 8.85 g of sintered product were obtained.
- the samples are prepared by separately introducing a manganese nitrate and a doping solution (aluminum and / or cobalt nitrate) into an initial solution of LiOH and NH 3 .
- the samples are transferred to a furnace without washing process and predried at 160 0 C static.
- the following is a Preliminary heat treatment of the precursor at 500 0 C.
- the intermediate product is vermörsert and in a second annealing step at different final temperatures (690 0 C, 73O 0 C and 770 0 C) was transferred to the end product.
- the crystallite size of the aluminum-doped spinels is significantly smaller.
- the derivatives of the potential curves (dQ / dE vs. E) were plotted (FIG. 1) in order to be able to better compare the expression of the potential levels.
- the maxima / minima correspond to the plateaus in the charging curves. The sharper the peaks are formed here, the stronger the step characteristic.
- FIG. 1 shows that, as the aluminum content in the structure increases, the peaks merge more closely with one another, which results in an increase in the size of the peaks
- the preparation of the mixed oxide according to the invention was prepared starting from a stoichiometric doped lithium manganese spinel (Precursorwert) obtained analogously to Comparative Example 1.
- a stoichiometric doped lithium manganese spinel Precursorwert
- LiOH stoichiometric doped lithium manganese spinel
- boron-oxygen compound of boron oxide in the form of a mixture of LiOH and B 2 O 3
- the addition of the boron-oxygen compound, in this case the borate, has an effect on the morphology, the half-widths of the X-ray reflections and the BET surface area of the Al / Li-doped lithium manganese spinels of the mixed oxide according to the invention.
- the crystallite size increases sharply upon addition of borate and increase in annealing temperature.
- the largest crystallites are thus achieved at a temperature of 770 0 C and with the addition of 1 wt .-% (preferably to the total mixture of the mixed oxide).
- the investigated mixed oxides according to the invention were monophasic (homophasic or homoeotypic) according to the profile of the XRD reflexes, i. a complete regular aluminum incorporation into the crystal structure had taken place.
- the XRD spectrum of the mixed oxide according to the invention (MOl 1% by weight borate and M02 0.5% by weight borate), obtained according to Example 1, was obtained with the XRD spectra of Al-doped superstoichiometric lithium manganese spinels obtainable according to Comparative Example 1 (M29 and M30 ) ( Figure 2).
- the presence of a boron-oxygen compound, here the borate, obtained in the mixed oxide according to the invention, according to Example 1 has a positive effect.
- the cycle stability increases, as can be seen from FIG. 6, with increasing borate content in the mixed oxide compared to a pure Al-doped lithium manganese spinel.
- the lithium superstoichiometry of the spinel component of the mixed oxide was varied stepwise at constant Al content.
- the two structural limit cases can be represented as follows:
- FIG. 9 shows dQ / dE vs E of materials of different mixed oxides according to the invention with different lithium stoichiometries.
- FIG. 10 compares the discharge capacities of samples of mixed oxides according to the invention in the first cycle.
- the theoretical value was calculated from the analytically determined spinel stoichiometry.
- the measured values are between 117 mAh / g for a pure lithium-doped (superstoichiometric) sample (EXM 1666) and 96 mAh / g for a Li / Al / Zn doped.
- the samples showed comparatively low capacities, which can be attributed to the increased lithium incorporation.
- FIG. 11 shows an overview of the potential profiles of the sample samples in the first full cycle.
- attention is paid to potential areas which gave the first indications of the cycling behavior of the samples.
- Both the appearance an additional potential level at 3.2 VaIs also a well-defined level at half charge / discharge are considered characteristic of bad cycle stability:
- stirrer batches were combined in a stirred feed tank and the still pumpable suspension was dried in a Storck Bowen spray dryer with two-fluid nozzle and atomization from above in a DC process at an air inlet temperature of 550 0 C and an air outlet temperature between 140 0 C and 145 ° C. , A brown powder with a bulk density of 1011 g / l was obtained.
- the resulting drying product still contains nitrates and was calcined on stainless steel Hordenblechen in a continuous belt furnace with connected exhaust gas purification plant for nitrous gases at 450 0 C and an average residence time of 1 h in the heating zone. Surprisingly low amounts of nitrous gases were developed and a fine black powder with a bulk density of 823 g / l was obtained.
- the calcination product was then annealed in an Alsint ceramic crucible in the chamber furnace in air at 770 0 C for 12 h at a heating time of 6 h and a cooling time of 12 h.
- the bluish black annealed product was ground on an Alpine AFG100 sifting air mill with ceramic sifting wheel and ceramic mill air nozzles of 3.0 mm diameter at a classifier speed of 5500 rpm.
- the ground product collected in the separation cyclone had a bulk density of 1045 g / l and a vibratory weight of 1713 g / l.
- Figure 13 is a scanning electron micrograph of the product.
- the chemical composition determined by ICP was:
- Residual moisture 0.26% by weight (Karl Fischer method)
- Surface area according to BET ⁇ lm 2 / g
- the mixed oxide containing lithium manganese spinel of the invention exhibits a discharge capacity of 105 mAh / g and a cycle loss of less than 0.1% per cycle measured in a half cell of the type LMS // LiPF6-EC-DMC // Li.
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Abstract
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DE102008029804A DE102008029804A1 (de) | 2008-06-24 | 2008-06-24 | Mischoxid enthaltend einen Lithium-Mangan-Spinell und Verfahren zu dessen Herstellung |
PCT/EP2009/004512 WO2009156119A1 (fr) | 2008-06-24 | 2009-06-23 | Mélange d'oxydes contenant un spinelle lithium-manganèse et son procédé de fabrication |
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US (3) | US9281522B2 (fr) |
EP (1) | EP2304828B1 (fr) |
JP (3) | JP2011525470A (fr) |
KR (1) | KR101365578B1 (fr) |
CN (2) | CN102067364A (fr) |
CA (1) | CA2728141C (fr) |
DE (1) | DE102008029804A1 (fr) |
TW (1) | TWI466829B (fr) |
WO (1) | WO2009156119A1 (fr) |
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JP2012116746A (ja) * | 2010-11-10 | 2012-06-21 | Jgc Catalysts & Chemicals Ltd | スピネル型リチウム・マンガン複合酸化物 |
KR101264333B1 (ko) * | 2011-01-12 | 2013-05-14 | 삼성에스디아이 주식회사 | 양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법 |
JP6292738B2 (ja) * | 2012-01-26 | 2018-03-14 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池 |
CN102903905A (zh) * | 2012-10-09 | 2013-01-30 | 江苏科捷锂电池有限公司 | 锌掺杂尖晶石正极材料的制备方法 |
US9905851B2 (en) | 2013-07-26 | 2018-02-27 | Lg Chem, Ltd. | Cathode active material and method of preparing the same |
US9905850B2 (en) | 2013-07-26 | 2018-02-27 | Lg Chem, Ltd. | Polycrystalline lithium manganese oxide particles, preparation method thereof, and cathode active material including the same |
JP6066534B2 (ja) * | 2013-07-26 | 2017-01-25 | エルジー・ケム・リミテッド | 多結晶リチウムマンガン酸化物粒子、その製造方法及びこれを含む正極活物質 |
JP6275593B2 (ja) * | 2013-09-24 | 2018-02-07 | 株式会社東芝 | リチウムイオン二次電池用負極活物質材料及びその製造方法、リチウムイオン二次電池、電池パック、並びに自動車 |
KR102406423B1 (ko) | 2013-10-04 | 2022-06-08 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 리튬 망가니즈 복합 산화물, 이차 전지, 및 전자 기기, 및 층의 형성 방법 |
US9960423B2 (en) * | 2013-11-22 | 2018-05-01 | Mitsui Mining & Smelting Co., Ltd. | Spinel-type lithium metal composite oxide |
JP2019016428A (ja) * | 2017-07-03 | 2019-01-31 | Basf戸田バッテリーマテリアルズ合同会社 | 非水電解質二次電池用正極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池 |
CL2017002221A1 (es) * | 2017-09-01 | 2018-01-19 | Univ Antofagasta | Espinela de manganeso dopada con magnesio, material catódico que la comprende, método de preparación, y batería de ion litio que la comprende |
JP2020518960A (ja) * | 2017-10-11 | 2020-06-25 | エルジー・ケム・リミテッド | 正極活物質、その製造方法、及びそれを含むリチウム二次電池 |
KR102656223B1 (ko) | 2017-11-22 | 2024-04-11 | 주식회사 엘지에너지솔루션 | 리튬 이차전지용 양극활물질 및 그 제조방법 |
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CN110790315A (zh) * | 2019-02-22 | 2020-02-14 | 重庆大学 | 一种锂离子电池正极Li4Mn5O12纳米颗粒的制备方法 |
CN110492097B (zh) * | 2019-08-30 | 2021-04-27 | 中南大学 | 一种ncm三元复合正极材料及其制备和应用 |
GB201916198D0 (en) * | 2019-11-07 | 2019-12-25 | Johnson Matthey Plc | Cathode material and process |
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JP6175177B2 (ja) | 2017-08-02 |
US20160068991A1 (en) | 2016-03-10 |
TW201008879A (en) | 2010-03-01 |
WO2009156119A1 (fr) | 2009-12-30 |
JP6054284B2 (ja) | 2016-12-27 |
US20170179485A1 (en) | 2017-06-22 |
TWI466829B (zh) | 2015-01-01 |
CN102067364A (zh) | 2011-05-18 |
CA2728141C (fr) | 2019-01-29 |
EP2304828B1 (fr) | 2018-10-31 |
CA2728141A1 (fr) | 2009-12-30 |
KR101365578B1 (ko) | 2014-02-20 |
US20110287319A1 (en) | 2011-11-24 |
DE102008029804A1 (de) | 2010-07-08 |
JP2017081819A (ja) | 2017-05-18 |
JP2011525470A (ja) | 2011-09-22 |
US9562303B2 (en) | 2017-02-07 |
US9281522B2 (en) | 2016-03-08 |
KR20110036897A (ko) | 2011-04-12 |
JP2014111533A (ja) | 2014-06-19 |
US10483538B2 (en) | 2019-11-19 |
WO2009156119A8 (fr) | 2010-03-18 |
CN107840343A (zh) | 2018-03-27 |
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